“Will alternative absorbent - Ian Davenportdavenportinternational.com/Outlook Sep 2015 FINAL.pdf · 2020-01-27 · “Will alternative absorbent polymers ever be Super for use in

“Will alternative absorbent

polymers ever be Super for use in

hygiene?’

Ian Davenport

(C) Davenport International Associates September 2015

[email protected]

www.davenportinternational.com

917-605-1174

1

mailto:[email protected]

http://www.davenportinternational.com/

PURPOSE

Overview of history, current status and future outlook for alternative (Super) absorbent polymers

(C) Davenport International Associates September 2015 2

AGENDA

• A confusing maze of definitions –

designed to obfuscate?

• Some common misconceptions

• What is on offer?

• The impact of lower oil

• Will alternative polymers ever be

competitive in hygiene applications?


Terminology

Renewable

Green

Biodegradability

Biocompatible

Super absorbent polymer


Biodegradable (Mirriam Webster)

adjective bio·de·grad·able \-di-ˈgrā-də-bəl\

: capable of being slowly destroyed and broken

down into very small parts by natural

processes, bacteria, etc.

Simply: can be reduced to carbon dioxide,

methane, & water


Renewable

adjective re·new·able \-ˈnü-ə-bəl, -ˈnyü-\

: able to be extended for another time period

: able to be renewed

: restored or replaced by natural processes :

able to be replaced by nature

Simply: made from a source that can be

renewed in nature (plant etc.)


Candidates for review?

• Starch blends

• ‘Natural polymers’

• Sodium polyacrylate from renewable AA

• Other chemistries


Starch Blends:

LYSAC (ADM) – carboxyalkyl cellulose

polymer and starch polymer blended in

water


ADM/ LYSAC• Canadian Groupe Lysac acquired 2006

• SNAP = Safe Natural Absorbent Polymer

• Patents covering “starch networks as

superabsorbent materials and their

preparation by extrusion”

• & “superabsorbent surface-treated

carboxyalkylated polysaccharides and process

for producing same”

• No recent data sheets available – last from

2009



“Natural” polymers

• ADM/ Chemanex JV SL

• Tethis

• Vitallico

• Other


Chemcel Pvt Ltd. Sri Lanka

ADM/ Chemanex JV to produce BioSAP ™

for sale by ADM

Announced August 2013

Plant reported to be ready for operation

No products offered to the market as yet


TETHIS

Goal:

To create a bio-polymer based SAP

that is adopted by the diaper industry


TETHIS

Initial Performance target:

CRC > 28 g/g

AUL (0.7 psi) > 15 g/g

Current values?

Long term target:

to achieve performance competitive

with conventional SAP


0

5

10

15

20

25

30

35

Jan-15 Mar-15 May-15 Jul-15 Sep-15 Nov-15 Jan-16

Perf

orm

an

ce (

g/g

)

Performance Progress

Performance Momentum: CRC

September 25, 2015 Copyright Tethis 2014, All Rights Reserved 15

Band of Market

ImplementationBand of Initial

Market Interest

~520% performance

improvement in 5 months

Additional 20-40% improvement

expected over following 2 months

TETHIS


Initial Target g/g Actual 31st Aug.

2015 g/g*

CRC 28 31.0

AUL 0.7 psi 15 13.6

*Tethis results

TETHIS

Moving fast, but a long way to go…still at

small scale…

Will use toll manufacturing to scale up and

prove the process

Extrusion process = possible fast scale up

with known manufacturing technologies


TETHIS

Other benefits:

- Renewable raw materials

- Fast absorption

- High Ionic tolerance

- Biodegradable

- Novel forms possible (fiber, foam,

films?)


VITALLICO

WO 2011/ 038374 Xiong et.al.

“Absorbent Composition & Methods

Thereof”

Natural Hydrocolloids treated with

porous Aluminum Silicate


VITALLICO

Approached Davenport 2 years ago,

has since disappeared


OTHER CHEMISTRIES?

Variety of polymers promoted for

Agriculture applications e.g.

Potassium Polyacrylate

PAM polymers

MCMC/HEC based polymers


What about Sodium Polyacrylate

SAP from ‘renewable’ AA?

• Impurities may differ according to

feedstock used

• Several projects


Sodium Polyacrylate from ‘renewable’ AA

• ADM

• Arkema

• Nippon Shokubai

• Cargill/ Novozyme

• Myriant

• Novomer


ADM : Direct Replacement of Chemicals

• Successful Propylene Glycol Project running

in Decatur since 2011

• Acrylic Acid - DOE grant $25 MM plus ADM

investment

• Proprietary technology to separate cellulose,

hemi-cellulose & lignin into individual

components then utilized for fuel & chemical

production

• ADM target is to produce cellulosic ethanol &

acrylic acid/ esters



Source: DOE Feb 2011, Biomass Program Peer Review

ARKEMA

1) Glycerol to acrylic acid reported 2009

collaboration

2) Arkema & HTE (High throughput

experimentation) Germany to screen

catalysts


NIPPON SHOKUBAI

IHS PERP – Process Economics Report

2011 – also cites Nippon Shokubai work

Nippon Shokubai had project for AA in

Indonesia based on Palm Oil


CARGILL

Aug. 2012:Cargill partnered with BASF/

Novozyme

July 2013: 3-hydroxypropionic acid (3-HP), one

possible precursor to acrylic acid, made at pilot

scale.

Sep 2014: successfully converted 3-HP to GAA

and SAP


CARGILL

Jan 2015: BASF to exit 3-way partnership

Why?

We can speculate…


CARGILL

April 2015: acquires OPX Bio….


OPX BIO

Startup based Boulder, CO

OPXBIO ‘provides more sustainable value to

customers by applying its proprietary EDGE ™

(Efficiency Directed Genome Engineering)

technology to produce economic, bio-based

chemicals that directly replace existing

petroleum-based products’


OPX BIO

April 2011: collaborate with Dow to ‘develop industrial

scale process for the production of bio-based acrylic

acid from renewable feedstocks.’

April 2013: collaborate with Evonik to ‘develop certain

bio-based specialty chemicals.’

Sep 2014: cooperation with Dow ended

April 2015: acquired by Cargill



Source: Biofuels Digest April 2015

CARGILL

April 2015: acquires OPX Bio…

Why?

• to give Cargill an option on a platform of

chemical production technology &

compete with ADM?

• Because BASF don’t want to use

renewable feedstock?


What about other routes to

‘renewable’ AA?

• Myriant

• Novomer


Myriant

Chemicals from dextrose with Succinic

Acid plant in Lake Providence, LA

Lactic acid to Acrylic acid route is

progressing quickly in the product pipeline

Collaboration with Penn State University

& MIT


Myriant – tech. claims 06/2015

At lab. scale achieved:

• 90% conversion of lactic acid

• > 80% selectivity for Acrylic acid

• 1 easily separated and marketable

by product

• Other by products at ppm level

• Stable catalyst performance


Myriant – status as of 06/2015

• Funded to end 2015

• Well supported by PTTGC (Thailand)

• In discussions with potential partners

based in EU & Asia


Myriant – next steps

• Scale up reactor with technical support

by PTTCG

• Produce samples for customer testing (1

& 2 levels of customer need to approve)

• Confirm catalyst life

• Find partner(s) for full scale

manufacturing and/ or license

agreements


Novomer AA via Propiolactone


Source: www.novomer.com

Novomer AA via Propiolactone


Source: www.novomer.com

Claims:

• Low capital processes

• Easy to ship Propiolactone

Novomer Latest:


The three co-founders of Novomer, a

startup company based on Cornell

research, have received the 2016 Kathryn

C. Hach Award for Entrepreneurial

Success from the American Chemical

Society (ACS), the society has announced.

Sodium Polyacrylate from

‘renewable’ AA

a) Provided GAA is ‘drop in’ then SAP

should meet all performance criteria

b) It will not be biodegradable SAP

c) What new impurities may be present?


Other chemistries

Exotech Bio Solutions“Exotech manufactures biocompatible and

biodegradable superabsorbent polymers (SAP) for

use in the personal hygiene, pharmaceuticals, food,

environmental and agriculture markets. ExoSAP has

the same absorbent properties as the competition, yet

has the advantage of being bio degradable as well as

being cheaper to produce.”

Zvika Meiri, CEO, Society of Plastics Engineers, Clean Technology Business Forum & Competition: GPEC® 2009


Exotech Bio Solutions

Variations on poly(styrene-co-maleic

anhydride/acid) with patents 1970 – 2011

(not all related to SAP)

e.g. Biocompatible, Biodegradable, water-

absorbent material and methods for its

preparation

US 20020193516 (Dec.2002 Bucevski &

Colt)



Independent test 2007

CRC 34 g/g

AUL 0.7 psi 22 g/g

PSD somewhat large (60% > 900 µ)

University COIMBRA (Portugal) Biodegradation

test OECD 310 positive results

So why no progress?



Chicken & Egg:

No investment = no larger scale production

No production = no large quantities for diaper

trials

No diaper trials = no proof of performance

No proof of performance = no investment



Chicken & Egg:


Production

Diaper

Trials

PoP*

Financing

* Proof of Performance


• 10-15 years of search for partners to invest

and commercialize

• Too soon?

• Focus now appears to be on Gelesis with $60

MM IPO filed April 1st 2015

‘weight loss capsule for patients with

obesity & type 2 diabetes’


Are there other possible chemistries for

SAP with similar carboxyl functionality?

• Aspartic acid

• Itaconic acid

• Glutamic acid


Other chemistries

Similar carboxyl functionality


Acrylic Acid 1:1

Aspartic acid 1:1

Itaconic acid 1:2

Glutamic Acid

Polyaspartic acid

Donlar Biopolymers – early 2000’s

CRC – high teens

AUL – low teens

Off color (yellow/ brown…)


Polyaspartic acid – other

references

• EP 0 866 084 A2 Production process of cross-linked

polyaspartic acid resin (1998, Irizato et.al. Mitsui)

A process is disclosed for producing with good

productivity a cross-linked polyaspartic acid resin having

biodegradability and high water absorbency

• Novel Superabsorbent Composite Based on

Poly(Aspartic Acid) and Organo-Kaolin - Journal of

Macromolecular Science, Part A: Pure and Applied

Chemistry Volume 51, Issue 10, 2014


http://www.tandfonline.com/loi/lmsa20?open=51#vol_51

http://www.tandfonline.com/toc/lmsa20/51/10

Itaconic acid

Itaconix – New Hampshire based start up


Itaconix

Need to use dual carboxyl function

5 new products close to launch markets oil

& gas, emulsions, detergents, others

Sodium polyacrylate works very well for

SAP

Hygiene customers will not, in our view,

pay extra for renewable or biodegradable(C) Davenport International Associates September 2015 55

REMINDER:

Natural or Renewable does not equal

‘Biodegradable’

Sodium polyacrylate SAP will have the

same profile physically and chemically

whatever the feedstock used for the acrylic

acid


What is Biodegradable?

OECD Test Guidelines No. 301 A-F:

DOC Die-Away Test (TG 301 A),

CO2 Evolution Test (TG 301 B),

Modified MITI Test (I) (TG 301 C),

Closed Bottle Test (TG 301 D),

Modified OECD Screening Test (TG 301 E)

Manometric Respirometry Test (TG 301 F)


What is Biodegradable?

OECD Test Guidelines No. 301 A-F:

The following pass levels of biodegradation,

obtained within 28 days, may be regarded as

evidence of ready biodegradability: 70% DOC

(dissolved organic carbon) removal (TG 301 A and

TG 301 E); 60% theoretical carbon dioxide

(ThCO2) (TG 301 B); 60% theoretical oxygen

demand (ThOD) (TG 301 C, TG 301 D and TG

301 F).


Does modified Sodium Polyacrylate

meet this standard?

NO

Higher starch = improved degradation = lower

SAP performance

Also, starch modified SAP tends to discolor


So What about ‘Low Oil’? (1)

• Equivalence is constantly changing

• Corn $6 v. Oil $100 was attractive for

some (but both volatile…)

• Long term pressure on global food chain

• Forecast excess of propylene will depress

SAP price (July 2015 already < 40 cpp in

US)(C) Davenport International Associates September 2015 60

So What about ‘Low Oil’? (2)

Low Propylene is an added challenge for

Biobased Acrylic Acid



FT Commodities Global Summit 04/21/2015

China’s taste for meat forces state grain trader to go global in search of feed

GREGORY MEYER — LAUSANNEThe head of Cofco, the Chinese state-owned grain trader, has laid out

plans to turn the company into a publicly listed global powerhouse,

highlighting Beijing’s decision to relax its policy of food self-sufficiency.

Ning Gaoning, Cofco chairman, told a Financial Times conference in

Lausanne that China’s farm imports would rise from 120m tonnes to

200m** tonnes in a decade as people consumed more meat and milk.

“This is a transformation period in China,” he said.

The diets of the country of 1.4bn have changed as living standards rose

with industrialisation. More meat and dairy on tables has strained arable

land and water resources, pushing China abroad in search of grain to feed

livestock.

** 1 MT meat requires 2-6 MT grain!

Conclusions

• No imminent threat to conventional Propylene

based SAP

• Agricultural commodity giants are moving

downstream into chemicals

• ‘Renewable’ feedstock will face cost pressure if it

competes with human food chain

• One or two startups may present credible future

alternatives with cost base other than Propylene –

YES, they might be eventually competitive BUT

the installed SAP capacity base is a huge barrier

to new entrants


Acknowledgments:

Absorbent Technologies, Inc.

Archer Daniels Midland Company*

EDANA

Ekotec GmbH

Hy-Tec GmbH

Exotech Bio Solutions Ltd.

Itaconix Corp.

Myriant Corp.

Nanochem Solutions Inc.*

Novomer Inc.

OPX Bio

Tethis Inc.

Vitalico LLC.*

Yixing Danson Science & Technology Co., Ltd.* Unavailable or unwilling to contribute


Thank you

Ian Davenport


[email protected]

www.davenportinternational.com

917-605-1174

65

mailto:[email protected]

http://www.davenportinternational.com/

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“Will alternative absorbent - Ian Davenportdavenportinternational.com/Outlook Sep 2015 FINAL.pdf · 2020-01-27 · “Will alternative absorbent polymers ever be Super for use in